CN102226051B - Glaze coloring agent for waterborne woodenware coating and preparation method thereof - Google Patents
Glaze coloring agent for waterborne woodenware coating and preparation method thereof Download PDFInfo
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Abstract
A glaze coloring agent for waterborne woodenware coating and a preparation method thereof belong to the coating field. The coloring agent comprises a color-spreading component and a color-fixing component. The color-spreading component comprises amphiphilic polymer resin which has the effect of pigment loading and bonding, and can allow the pigment to spread and penetrate on a wood surface; the color-fixing component comprises acrylate polymer which has excellent color retention and weatherability. The coloring agent of the invention can provide proper open time for construction, can be rewiped, is easy for color modification, has good color retention for recoating, does not cause floating color or loose color, has good compatibility and interlayer binding force with various waterborne priming paint and top finish, and can well improve the wood-grain contrast of a wood surface; with the matching application of various waterborne woodenware coating processes, the coloring agent has the characteristics of safety and environmental protection, no irritant smell, uniform coloring, plump filling, and excellent color fixing; by adjusting the ratio of the color-spreading component and the color-fixing component, the coloring agent is applicable to waterborne coloring and American antique coating processes of various wood furniture products.
Description
Technical field:
The present invention relates to a kind of Ge Lisi wiping stain for coating aqueous carpentry and preparation method thereof.
Background technology:
Water-borne wood coating be a kind of brushing at the coating products of wood furniture or wood product surface, except possessing the provide protection to timber-work, also need to have certain decorative effect.In the coating process of water-borne wood coating, American and European style technique is occupied very important position.American and European style is a kind of open application, by deepening the wood grain contrast gradient, strengthens the gradation sense of wood surface and stereoscopic sensation and the natural vein of timber is fully highlighted, and brings the texture of natural beauty to furniture.American and European style claims again antique coating, by coordinating some special sheet materials processing and wiping look technique as old in doing, worm channel destroys processing etc., can also obtain the decorative effect close to the European pseudo-classic furniture of paintable finish, thereby greatly promote the commodity value of wood furniture.
The wiping stain and the tinting material product that are used for traditional American and European style technique mostly are solvent type Synolac, non-drying vegetables oil and some Water-borne modification products that occur recently such as modified linseed oil type timber wiping stain etc.Synolac class wiping stain is such as patent CN 101472686A, owing in use needing to add thinner to cause bad impact to workmen's health; For non-drying plant oil product and watersoluble modified product thereof, although on the color development effect better such as patent CN1810898A, CN101608079A, CN101386726A, drying is slow, the fixation tint retention is poor but exist, and relatively poor with the consistency of water-borne coatings, can't with the good combination of aqueous priming paint or aqueous finish paint, the colour contamination problem such as grow dim very easily appears in follow-up application.There is in addition a class emulsion-type to be used for the molten multistage resin of translucent painted alkali as described in patent CN1090290A, the problems such as color development poor-performing and swelling wood surface are arranged, be difficult to the decoration requirement that reaches higher.
Summary of the invention:
The present invention prepares by the structure design of high molecular polymer the novel aqueous woodwork coating tinting material that is specifically designed to water-borne wood coating.This tinting material has excellent color developing and suitable open hour, pigment well can be brought in wiping the look process in the groove of wood surface with fiber mechanism in, uniform coloring and recoverability are strong, can fully improve aberration and the contrast gradient of wood grain; Simultaneously, its tint retention and interlayer adhesion are excellent, and dry can not damaging the ground color in colored surface recoat process later colour contamination or loose colour can not occur, the face of being equipped with repair more making after look technique wood figure and the pinhole lines clear, the wood furniture color that obtains is plentiful and lively.This timber use wiping stain tint retention is splendid, and the life-time service nondiscoloration reaches the decorative effect that compares favourably with the molten type wiping stain of traditional oils on painting effect, and has than the better feature of environmental protection and security when using.
the invention provides a kind of Ge Lisi wiping stain for coating aqueous carpentry, it is characterized in that, described Ge Lisi wiping stain is comprised of color development component and fixation component, wherein the color development component concentration is 50～90% of Ge Lisi wiping stain total mass, the fixation component concentration is 10～50% of Ge Lisi wiping stain total mass, the color development component comprises a kind of amphiphilic fluoropolymer resin that consumption is Ge Lisi wiping stain total mass 15～30%, the mixture of 5～30% pure and mild ether, 0.5～1% thickening material, 0.5～5% dispersion agent, 0.1～1% anti-settling agent, 1～8% aqueous color paste or water-based toner, and 6～12% deionized water, the fixation component comprises a kind of acrylic ester polymer that consumption is Ge Lisi wiping stain total mass 1.5～15%, the mixture of 5～20% pure and mild ether, 0.1～1% defoamer and 9～13% deionized water,
Described amphiphilic resin is obtained by radical copolymerization by esters of acrylic acid hard monomer, esters of acrylic acid soft monomer and function monomer, wherein the consumption of function monomer proportion in the resin total mass is 3～50%, and contains the acrylic or methacrylic acid mono that accounts at least function monomer total mass 6% in function monomer total amount used; The consumption mass ratio of said esters of acrylic acid hard monomer and esters of acrylic acid soft monomer is 40～80: 20～60; Wherein the esters of acrylic acid hard monomer is a kind of in following material or their combination: methyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, β-dimethyl-aminoethylmethacrylate, Tert-butyl Methacrylate; The esters of acrylic acid soft monomer is a kind of in methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, n-BMA, lauryl methacrylate(LMA), alkyl methacrylate or their combination; Function monomer is a kind of in following material or their combination: Sodium styrene sulfonate, acrylic amine ethyl ester, methacrylic acid-N, and N-dimethyl ethyl ester, 2-vinyl pyridine or 4-vinylpridine, vinyl piperidines, acrylamide, Methacrylamide, N-replace (methyl) acrylamide, diacetone-acryloamide(DAA), vinyl-acetic ester, vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, vinylformic acid, α-methacrylic acid;
Described amphiphilic resin adopts the semi-batch method synthetic, and synthesis step is as follows:
adding quality in the reaction vessel that whipping appts and reflux cooler are housed of temperature controllable heating is the deionized water of 0.1～0.8 times of reaction monomers, 0.05 the mixture of the ether of pure and mild 0.1～0.5 times of～0.5 times is as reaction medium, adopt nitrogen protection and condensate return, after being warming up to temperature of reaction and backflow occurring, add the esters of acrylic acid hard monomer in bottle, the mixture of esters of acrylic acid soft monomer and function monomer and n-dodecyl mercaptan, wherein all kinds of monomer masses used are respectively 5～15% of the quality that always feeds intake separately, the n-dodecyl mercaptan consumption is all reaction monomers 0.1～1% of total mass that feeds intake, and be incorporated as the initiator initiated polymerization of all reaction monomers total masses 0.5～1%, after 10 minutes again with the mixture of remaining esters of acrylic acid hard monomer, esters of acrylic acid soft monomer and function monomer be the n-dodecyl mercaptan of all reaction monomers total masses 0.5～3%, and be added dropwise in reaction vessel simultaneously with feeding device for the initiator of all reaction monomers total masses 0.5～1%.After dropwising, raise 5～10 ℃ and carry out insulation reaction, be cooled to afterwards below 40 ℃, add pH adjusting agent to regulate pH value to 7～8, continue to stir and cooling discharge, obtain amphiphilic fluoropolymer resin;
Described acrylic ester polymer carries out the free radical emulsion copolymerization by multiple vinyl monomer and obtains, contain alkene class hard monomer, alkene class soft monomer and function monomer in monomer for the preparation of acrylic ester polymer, its quality amount ratio is 35～60: 40～70: 2～10;
Described alkene class hard monomer is a kind of in methyl methacrylate, isobornyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, β-dimethyl-aminoethylmethacrylate, Tert-butyl Methacrylate, vinylbenzene or their combination; Alkene class soft monomer is a kind of in methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, n-BMA or their combination; Function monomer is one or more the composition that acrylic amine ethyl ester, acrylamide, Methacrylamide, N-replace (methyl) acrylamide, diacetone-acryloamide(DAA), vinyl-acetic ester, vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, vinylformic acid, methacrylic acid.
Described acrylic ester polymer adopts semicontinuous-seed emulsion polymerization synthetic, and synthesis step is as follows:
under nitrogen protection, to thermometer is housed, whipping appts, in the reaction vessel of the temperature controllable heating of reflux cooler and feeding device, add emulsifying agent and deionized water, open and stir, add after 5 minutes and contain alkene class hard monomer, the mixture of alkene class soft monomer and function monomer carries out pre-emulsification, wherein all kinds of monomer masses used are respectively 1～10% of the quality that always feeds intake separately, the pre-emulsification time is 15 minutes, then be heated to temperature of reaction, be incorporated as the initiator initiated polymerization of reaction monomers total mass 0.05～0.25%, initiator needs with adding reactor after deionized water dissolving, when refluxing no longer appears in system, begin to prepare to add remaining reaction monomers mixture, comprising alkene class hard monomer, alkene class soft monomer and function monomer, above-mentioned reaction monomers mixture and the deionized water solution of initiator are dripped simultaneously, add in reaction vessel, wherein initiator amount is reaction monomers total mass 0.05～0.25%, then 5～10 ℃ of insulation reaction that after reinforced complete, temperature control raise 2～3 hours are cooled to below 40 ℃, add pH adjusting agent to regulate pH value to 7～8, filter discharging, obtain acrylic ester polymer.
The mixture of pure and mild ether used, wherein alcohol is one or more in ethanol, ethylene glycol, 1,3-PD, 1,2-PD, BDO, Virahol, propyl carbinol and isopropylcarbinol; Ether is one or more in dipropylene glycol butyl ether, dipropylene glycol methyl ether and propylene glycol monomethyl ether.
A kind of as in benzoyl peroxide, azo-bis-isobutyl cyanide, vitriolate of tartar, Sodium Persulfate, ammonium persulphate, Sodium Persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite of the initiators for polymerization that the synthesis of amphoteric resin uses.
A kind of as in sodium hydroxide, potassium hydroxide, ammoniacal liquor, diethanolamine, trolamine and 2-amino-2-methyl-1-propanol of the pH adjusting agent that synthesis of amphoteric resin and acrylic ester polymer use.
Described acrylic acid synthesizing ester polymer emulsifying agent used is anionic, non-ionic type or negatively charged ion and non-ionic composite, perhaps reactive emulsifier.
The initiator that the acrylic acid synthesizing ester polymer uses is: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium Persulphate-sodium bisulfite, Sodium Persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite a kind of.
The preparation method of described Ge Lisi wiping stain for coating aqueous carpentry is characterized in that, step is as follows:
1. the mixture and the thickening material that add successively amphiphilic resin, deionized water, pure and mild ether under the dispersed with stirring effect, dispersed with stirring 20 minutes, continue to add aqueous color paste or water-based toner, wetting dispersing agent and anti-settling agent in said mixture, continue dispersed with stirring 30 minutes, and obtained the color development component of Ge Lisi wiping stain;
2. the mixture and the defoamer that add successively acrylate polymer emulsion, deionized water, pure and mild ether under the dispersed with stirring effect, dispersed with stirring 30 minutes obtains Ge Lisi wiping stain fixation component;
3. the fixation component that the color development component that obtains in inciting somebody to action 1. under the dispersed with stirring effect obtains in adding 2., dispersed with stirring discharging in 20 minutes.
Key of the present invention is, two kinds of polymkeric substance that are used for the Ge Lisi wiping stain preparation of coating aqueous carpentry have been synthesized in design, wherein a kind of polymkeric substance has the amphiphilic resin of color development and the effect of bonding pigment, simultaneously its polar group that contains makes in toning and drying process for the stability in solution system and consistency and all demonstrates the good transparency and permeability, another polymkeric substance has fast filming and fixing property, both has good consistency concurrently and makes the resulting woodstain can stably stored.Ge Lisi wiping stain of the present invention can be when the American and European style technique that is used for coating aqueous carpentry and other coloring process, demonstrate good consistency and interlayer bonding force with various aqueous priming paints, finish paint, colour contamination or decolouring can not occur in the good and recoat process of fixation tint retention, have excellent color developing and Xiu Se concurrently, the advantage such as have no irritating odor, be applicable to wood furniture and the goods of various material, essential in application.
Embodiment
The purpose of following embodiment is in order to further illustrate the present invention, in any case the present invention is not subjected to the restriction of these embodiment.
The abbreviation that may use in list
Embodiment 1
The preparation of acrylate polymer emulsion
passing under nitrogen protection, to thermometer is housed, whipping appts, in reflux cooler and dropping funnel 500mL four-hole boiling flask, add 2.52g reactive emulsifier allyl group polyethoxye sulfonate (SE-10N), 78mL deionized water (DI), open and stir 600 rev/mins, add the seed monomer after 5 minutes, comprise: butyl acrylate 4.54g, methyl methacrylate 6.81g, methacrylic acid 0.25g and 10mL contain water (DI) solution of acrylamide 1g, pre-emulsification 15 minutes, being warmed up to 82 ℃ occurs refluxing, add 10mL to contain initiator water (DI) solution of 0.32g ammonium persulphate, initiated polymerization, until no longer occur refluxing, begin to drip the residual monomer mixture, comprising: butyl acrylate 40.82g, methyl methacrylate 61.24g, methacrylic acid 2.27g and 35mL contain water (DI) solution of acrylamide 9.07g, drip simultaneously water (DI) solution that 40mL contains the 0.32g ammonium persulphate, time for adding is 2 hours.After mix monomer dropwised, rising system temperature to 87 ℃ was incubated 2 hours, was cooled to that to add the 3.3g volumetric concentration below 40 ℃ be that 25% ammoniacal liquor continues to stir, and regulated pH value to 7～8, filtered discharging.
The preparation of amphiphilic resin
with reflux cooler, the electric stirring oar, add 40g water (DI) in the 500mL four-hole boiling flask of thermometer and temperature controller and constant pressure funnel, 40g Virahol and 35g dipropylene glycol butyl ether, pass into nitrogen as protective atmosphere, use condensate return, after being warming up to 79 ℃ of appearance backflows, add the 6.62g butyl acrylate in reaction flask, 7.56g methyl methacrylate, 1.26g vinylformic acid, 0.53g the mixture of n-dodecyl mercaptan and 0.32g acrylamide, maintaining the temperature at 79 ℃ continues to add 10g to contain initiator water (DI) solution of 1.05g ammonium persulphate, initiated polymerization, after 10 minutes again with the 37.49g butyl acrylate, 42.84g methyl methacrylate, 7.14g vinylformic acid with add constant pressure funnel after the 1.06g n-dodecyl mercaptan mixes, the 1.79g acrylamide is dissolved in 20g water (DI), the 1.05g ammonium persulphate is dissolved in 40gmL water (DI), and with remaining monomer mixture, acrylamide water (DI) solution drips simultaneously, add in 3 hours, be warming up to 86 ℃, insulation reaction 2 hours, then be cooled to below 40 ℃, adding 10g to contain water (DI) solution of 2.7g sodium hydroxide and 2.9g volumetric concentration is that 25% ammoniacal liquor is regulated pH value to 7～8, continue to stir 10 minutes, then cooling discharge.
The preparation of Ge Lisi wiping stain
(1) add successively the amphiphilic resin of 70g, 12g deionized water, 10g1 under the dispersed with stirring effect of 600 rev/mins, ammediol and 0.5gPU-240 (association type polyurethane thickener), dispersed with stirring 20 minutes, continue to add the brown transparent iron oxide pigment mill base of 8g, 0.5gDISPERBYK-111 wetting dispersing agent and 0.5gBYK-410 anti-settling agent in said mixture, dispersed with stirring is 30 minutes under the condition of 2000 rev/mins, obtains the color development component of Ge Lisi wiping stain;
(2) add successively 50g acrylate polymer emulsion, 18g anhydrate (DI), 24g 1 under the rate of dispersion of 600 rev/mins of rotating speeds, ammediol, 8g Dipropylene glycol mono-n-butyl Ether and 0.5gBYK-024 defoamer, dispersed with stirring 30 minutes obtains Ge Lisi wiping stain fixation component;
(3) under the rate of dispersion of 600 rev/mins of rotating speeds, get the color development component that obtains in 60g (1) and join in the fixation component that obtains in 40g (2), dispersed with stirring discharging in 20 minutes.
The described method for producing polymer of embodiment 1-10 and monomer ratio are with embodiment 1, and difference is in the preparation of beautiful this wiping stain of dative, and wherein color development component and fixation component proportion are as shown in table 1-1; The described amphiphilic process for preparing resins of embodiment 11-20 is with embodiment 1, and monomer ratio is as shown in table 1-2, and the preparation method of described acrylate polymer emulsion and monomer ratio are with embodiment 1, and Ge Lisi wiping stain preparation method is also with described in embodiment 1; Parents' resin physical properties is as shown in table 1-2, and acrylic ester emulsion character is as shown in table 1-1;
Embodiment 21
The preparation of acrylate polymer emulsion
passing under nitrogen protection, to thermometer is housed, whipping appts, in reflux cooler and dropping funnel 500mL four-hole boiling flask, add 2.52g reactive emulsifier allyl group polyethoxye sulfonate (SE-10N), 78mL deionized water (DI), open and stir 600 rev/mins, add the seed monomer after 5 minutes, comprise: butyl acrylate 3.53g, methyl methacrylate 2.27g, methacrylic acid 0.13g and acrylamide 0.5g, pre-emulsification 15 minutes, being warmed up to 82 ℃ occurs refluxing, add 10mL to contain initiator water (DI) solution of 0.32g ammonium persulphate, initiated polymerization, until no longer occur refluxing, begin to drip the residual monomer mixture, comprising: butyl acrylate 67.03g, methyl methacrylate 43.09g and methacrylic acid 2.39g, drip simultaneously water (DI) solution that water (DI) solution that 40mL contains the 0.32g ammonium persulphate and 35mL contain acrylamide 9.58g, time for adding is 2 hours.After mix monomer dropwised, rising system temperature to 87 ℃ was incubated 2 hours, was cooled to that to add the 3.3g volumetric concentration below 40 ℃ be that 25% ammoniacal liquor continues to stir, and regulated pH value to 7～8, filtered discharging.
The preparation of amphiphilic resin
with reflux cooler, the electric stirring oar, add 50g water (DI) in the 500mL four-hole boiling flask of thermometer and temperature controller and constant pressure funnel, the 10g Virahol, 50g dipropylene glycol butyl ether and 50g1, the 2-propylene glycol, pass into nitrogen as protective atmosphere, use condensate return, after being warming up to 79 ℃ of appearance backflows, add the 4.8g butyl acrylate in reaction flask, the 6g methyl methacrylate, 0.96g vinylformic acid, 0.6g n-dodecyl mercaptan, 0.8g benzoyl peroxide and 0.24g acrylamide, maintain the temperature at 79 ℃ of initiated polymerizations, then with the 43.2g butyl acrylate, the 54g methyl methacrylate, 9.64g vinylformic acid 1.8g n-dodecyl mercaptan with add constant pressure funnel after the 1.6g benzoyl peroxide mixes, the 2.16g acrylamide is dissolved in 20g water (DI), drip simultaneously with mixture in dropping funnel, add in about 3 hours, insulation continues reaction 2 hours under 80～82 ℃, be cooled to below 40 ℃ after reaction finishes, adding 5.6g diethanolamine and 1.9g volumetric concentration is that 25% ammoniacal liquor is regulated pH value to 7～8, continues to stir 10 minutes, then cooling discharge.
The preparation of Ge Lisi wiping stain
(1) add successively the amphiphilic resin of 60g, 14g deionized water, 18g1 under the dispersed with stirring effect of 600 rev/mins, ammediol and 0.5gPU-240, dispersed with stirring 20 minutes, continue to add the brown transparent iron oxide pigment mill base of 8g, 0.5g DISPERBYK-111 wetting dispersing agent and 0.5gBYK-410 anti-settling agent in said mixture, dispersed with stirring is 30 minutes under the condition of 2000 rev/mins, obtains the color development component of Ge Lisi wiping stain;
(2) add successively 50g acrylate polymer emulsion, 18g deionized water, 30g1 under the rate of dispersion of 600 rev/mins, ammediol, 2g Dipropylene glycol mono-n-butyl Ether and 0.5gBYK-024 defoamer, dispersed with stirring 30 minutes obtains Ge Lisi wiping stain fixation component;
(3) the color development component that obtains in (1) under the rate of dispersion of 600 rev/mins is got the fixation component that 60g obtains in adding 40g (2), dispersed with stirring discharging in 20 minutes.
The preparation method of embodiment 21-25 is the same, and the proportioning of color development component and fixation component when difference is to prepare the Ge Lisi wiping stain is as shown in table 1-3; Identical in the acrylate polymer emulsion synthetic method of using in embodiment 26-35 and embodiment 21, the synthetic method of amphiphilic resin is identical, and monomer ratio is as shown in table 1-4;
In embodiment, some physical parameters of prepared acrylate polymer emulsion, amphiphilic resin are as shown in table 2-2, and acrylic ester emulsion character is as shown in table 1-1;
The performance estimating method of wiping stain and step
The Ge Lisi wiping stain that the present invention is used for coating aqueous carpentry can be applicable to that multiple difference is wooden, the American and European style technique of different decorative patterns and painted.The sample of each embodiment is wiped look performance evaluation, these staining tests are all to carry out on the Qu Liumu plate of 40cm * 30cm * 2cm through polishing, concrete operation method is: appropriate Ge Lisi wiping stain is poured on plank, with gauze according to the clockwise direction wiping of looping, wait for and heavily wipe and receive look after 5 to 10 minutes, polish after 30 minutes and repair look, white paint on recoat after 1 hour, estimate respectively wiping, heavily wiping property, the interlayer bonding force of repairing look, color developing, fillibility, fixation and recoat, evaluation result sees Table 3-1, table 3-2.
Wiping: wiping is smooth is 4 grades, and the stagnant hand of wiping is 0 grade, is divided into successively 5 grades;
Heavy wiping property: heavily wiping is easily 4 grades, and being difficult to heavily wipe is 0 grade, is divided into successively 5 grades;
Repair look: repairing the look gapless is 4 grades, and it is 0 grade that lapping defect is arranged, and is divided into successively 5 grades;
Color developing: it is 4 grades that color development evenly, is not grown dim, and painted growing dim is 0 grade, is divided into successively 5 grades;
Fillibility: it is 4 grades that wood grain is filled full, good contrast, and filling discontented or inhomogeneous, wood grain poor contrast is 0 grade, is divided into successively 5 grades;
Fixation: recoat not loose colour is 4 grades, and loose colour is seriously 0 grade, is divided into successively 5 grades.
Interlayer bonding force: mark the approximately intersection grid of 2mm of 5 groups of spacings with icking tool, tear after being affixed on the knurled surfaces compacting with scotch tape, be divided into successively 0 to 4 grade 5 with colorant dropping situations in grid etc.
Table 1-1
| Embodiment | Color development component/g | Fixation component/g | Embodiment | Color development component/g | Fixation component/g |
| 1 | 10 | 90 | 6 | 60 | 40 |
| 2 | 20 | 80 | 7 | 70 | 30 |
| 3 | 30 | 70 | 8 | 80 | 20 |
| 4 | 40 | 60 | 9 | 90 | 10 |
| 5 | 50 | 50 | 10 | 100 | 0 |
Table 1-2
Table 1-3
| Embodiment | Color development component/g | Fixation component/g |
| 21 | 20 | 80 |
| 22 | 40 | 60 |
| 23 | 60 | 40 |
| 24 | 80 | 20 |
| 25 | 100 | 0 |
Table 1-4
(1) in the table, listed formula is the actual usage quantity of each embodiment;
(2) in the table unlisted consumption with in embodiment 1, embodiment 21 and shown in explanation.
Table 2-1 (acrylate polymer emulsion physical property)
Table 2-2 (amphiphilic polymkeric substance physical property)
| Embodiment | pH | Outward appearance | Solid content | Embodiment | pH | Outward appearance | Solid content |
| 1 | 7.6 | Light yellow transparent | 0.347 | 21 | 7.3 | Water white transparency | 0.389 |
| 11 | 7.6 | Light yellow transparent | 0.335 | 26 | 7.3 | Water white transparency | 0.393 |
| 12 | 7.8 | Water white transparency | 0.339 | 27 | 7.5 | Water white transparency | 0.395 |
| 13 | 7.9 | Water white transparency | 0.345 | 28 | 7.3 | Water white transparency | 0.393 |
| 14 | 7.9 | Water white transparency | 0.340 | 29 | 7.4 | Water white transparency | 0.390 |
| 15 | 7.9 | Water white transparency | 0.347 | 30 | 7.5 | Water white transparency | 0.398 |
| 16 | 7.9 | Light yellow transparent | 0.340 | 31 | 7.7 | Water white transparency | 0.385 |
| 17 | 7.8 | Water white transparency | 0.343 | 32 | 7.4 | Water white transparency | 0.393 |
| 18 | 7.8 | Water white transparency | 0.347 | 33 | 7.5 | Water white transparency | 0.390 |
| 19 | 7.9 | Light yellow transparent | 0.340 | 34 | 7.4 | Water white transparency | 0.390 |
| 20 | 7.6 | Light yellow transparent | 0.339 | 35 | 7.4 | Water white transparency | 0.389 |
When (3) solid content finishes by reaction, sampling is surveyed;
(4) described outward appearance is regulated pH for reaction after finishing, estimate under 25 ℃ of room temperatures;
(5) the pH value is measured with accurate pH test paper after adding pH adjusting agent.
Table 3-1
Table 3-2
(6) operator's difference may be brought some differences in evaluation, but these differences are not enough to affect the evaluation of overall performance.
Claims (7)
1. Ge Lisi wiping stain that is used for coating aqueous carpentry, it is characterized in that, described Ge Lisi wiping stain is comprised of color development component and fixation component, wherein the color development component concentration is 50 ~ 90% of Ge Lisi wiping stain total mass, the fixation component concentration is 10 ~ 50% of Ge Lisi wiping stain total mass, the color development component comprises a kind of amphiphilic fluoropolymer resin that consumption is Ge Lisi wiping stain total mass 15 ~ 30%, the mixture of 5 ~ 30% pure and mild ether, 0.5 ~ 1% thickening material, 0.5 ~ 5% dispersion agent, 0.1 ~ 1% anti-settling agent, 1 ~ 8% aqueous color paste or water-based toner, and 6 ~ 12% deionized water, the fixation component comprises a kind of acrylic ester polymer that consumption is Ge Lisi wiping stain total mass 1.5 ~ 15%, the mixture of 5 ~ 20% pure and mild ether, 0.1 ~ 1% defoamer and 9 ~ 13% deionized water,
Described amphiphilic fluoropolymer resin is obtained by radical copolymerization by esters of acrylic acid hard monomer, esters of acrylic acid soft monomer and function monomer, wherein the consumption of function monomer proportion in the resin total mass is 3 ~ 50%, and contains the acrylic or methacrylic acid mono that accounts at least function monomer total mass 6% in function monomer total amount used; The consumption mass ratio of said esters of acrylic acid hard monomer and esters of acrylic acid soft monomer is 40 ~ 80:20 ~ 60; Wherein the esters of acrylic acid hard monomer is a kind of in following material or their combination: methyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, β-dimethyl-aminoethylmethacrylate, Tert-butyl Methacrylate; The esters of acrylic acid soft monomer is a kind of in methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, n-BMA, lauryl methacrylate(LMA), alkyl methacrylate or their combination; Function monomer is a kind of in following material or their combination: Sodium styrene sulfonate, acrylic amine ethyl ester, methacrylic acid-N, and N-dimethyl ethyl ester, 2-vinyl pyridine or 4-vinylpridine, vinyl piperidines, acrylamide, Methacrylamide, N-replace (methyl) acrylamide, diacetone-acryloamide(DAA), vinyl-acetic ester, vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, vinylformic acid, α-methacrylic acid;
Described amphiphilic fluoropolymer resin adopts the semi-batch method synthetic, and synthesis step is as follows:
adding quality in the reaction vessel that whipping appts and reflux cooler are housed of temperature controllable heating is the deionized water of 0.1 ~ 0.8 times of reaction monomers, 0.05 the mixture of the ether of pure and mild 0.1 ~ 0.5 times of ~ 0.5 times is as reaction medium, adopt nitrogen protection and condensate return, after being warming up to temperature of reaction and backflow occurring, add the esters of acrylic acid hard monomer in bottle, the mixture of esters of acrylic acid soft monomer and function monomer and n-dodecyl mercaptan, wherein all kinds of monomer masses used are respectively 5 ~ 15% of the quality that always feeds intake separately, the n-dodecyl mercaptan consumption is all reaction monomers 0.1 ~ 1% of total mass that feeds intake, and be incorporated as the initiator initiated polymerization of all reaction monomers total masses 0.5 ~ 1%, after 10 minutes again with the mixture of remaining esters of acrylic acid hard monomer, esters of acrylic acid soft monomer and function monomer be the n-dodecyl mercaptan of all reaction monomers total masses 0.5 ~ 3%, and be added dropwise to simultaneously in reaction vessel with feeding device for the initiator of all reaction monomers total masses 0.5 ~ 1%, after dropwising, raise 5 ~ 10 ℃ and carry out insulation reaction, be cooled to afterwards below 40 ℃, add pH adjusting agent to regulate pH value to 7 ~ 8, continue to stir and cooling discharge, obtain amphiphilic fluoropolymer resin,
Described acrylic ester polymer carries out the free radical emulsion copolymerization by multiple vinyl monomer and obtains, contain alkene class hard monomer, alkene class soft monomer and function monomer in monomer for the preparation of acrylic ester polymer, its quality amount ratio is 35 ~ 60:40 ~ 70:2 ~ 10;
Described alkene class hard monomer is a kind of in methyl methacrylate, isobornyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, β-dimethyl-aminoethylmethacrylate, Tert-butyl Methacrylate, vinylbenzene or their combination; Alkene class soft monomer is a kind of in methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, n-BMA or their combination; Function monomer is one or more the composition that acrylic amine ethyl ester, acrylamide, Methacrylamide, N-replace (methyl) acrylamide, diacetone-acryloamide(DAA), vinyl-acetic ester, vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, vinylformic acid, methacrylic acid;
Described acrylic ester polymer adopts semicontinuous-seed emulsion polymerization synthetic, and synthesis step is as follows:
under nitrogen protection, to thermometer is housed, whipping appts, in the reaction vessel of the temperature controllable heating of reflux cooler and feeding device, add emulsifying agent and deionized water, open and stir, add after 5 minutes and contain alkene class hard monomer, the mixture of alkene class soft monomer and function monomer carries out pre-emulsification, wherein all kinds of monomer masses used are respectively 1 ~ 10% of the quality that always feeds intake separately, the pre-emulsification time is 15 minutes, then be heated to temperature of reaction, be incorporated as the initiator initiated polymerization of reaction monomers total mass 0.05 ~ 0.25%, initiator needs with adding reactor after deionized water dissolving, when refluxing no longer appears in system, begin to prepare to add remaining reaction monomers mixture, comprising alkene class hard monomer, alkene class soft monomer and function monomer, above-mentioned reaction monomers mixture and the deionized water solution of initiator are dripped simultaneously, add in reaction vessel, wherein initiator amount is reaction monomers total mass 0.05 ~ 0.25%, then 5 ~ 10 ℃ of insulation reaction that after reinforced complete, temperature control raise 2 ~ 3 hours are cooled to below 40 ℃, add pH adjusting agent to regulate pH value to 7 ~ 8, filter discharging, obtain acrylic ester polymer.
2. the Ge Lisi wiping stain for coating aqueous carpentry according to claim 1, it is characterized in that, the mixture of pure and mild ether used, wherein alcohol is ethanol, ethylene glycol, 1, ammediol, 1, one or more in 2-propylene glycol, BDO, Virahol, propyl carbinol and isopropylcarbinol; Ether is one or more in dipropylene glycol butyl ether, dipropylene glycol methyl ether and propylene glycol monomethyl ether.
3. the Ge Lisi wiping stain for coating aqueous carpentry according to claim 1, it is characterized in that a kind of as in benzoyl peroxide, azo-bis-isobutyl cyanide, vitriolate of tartar, Sodium Persulfate, ammonium persulphate, Sodium Persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite of the initiators for polymerization that the synthesis of amphoteric fluoropolymer resin uses.
4. the Ge Lisi wiping stain for coating aqueous carpentry according to claim 1, it is characterized in that a kind of as in sodium hydroxide, potassium hydroxide, ammoniacal liquor, diethanolamine, trolamine and 2-amino-2-methyl-1-propanol of the pH adjusting agent that synthesis of amphoteric fluoropolymer resin and acrylic ester polymer use.
5. the Ge Lisi wiping stain for coating aqueous carpentry according to claim 1, it is characterized in that, described acrylic acid synthesizing ester polymer emulsifying agent used is anionic, non-ionic type or negatively charged ion and non-ionic composite, perhaps reactive emulsifier.
6. the Ge Lisi wiping stain for coating aqueous carpentry according to claim 1, it is characterized in that, the initiator that the acrylic acid synthesizing ester polymer uses is: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium Persulphate-sodium bisulfite, Sodium Persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite a kind of.
7. the preparation method of the Ge Lisi wiping stain for coating aqueous carpentry according to claim 1, is characterized in that, step is as follows:
1. the mixture and the thickening material that add successively amphiphilic fluoropolymer resin, deionized water, pure and mild ether under the dispersed with stirring effect, dispersed with stirring 20 minutes, continue to add aqueous color paste or water-based toner, wetting dispersing agent and anti-settling agent in said mixture, continue dispersed with stirring 30 minutes, and obtained the color development component of Ge Lisi wiping stain;
2. the mixture and the defoamer that add successively acrylate polymer emulsion, deionized water, pure and mild ether under the dispersed with stirring effect, dispersed with stirring 30 minutes obtains Ge Lisi wiping stain fixation component;
3. the fixation component that the color development component that obtains in inciting somebody to action 1. under the dispersed with stirring effect obtains in adding 2., dispersed with stirring discharging in 20 minutes.
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| CN 201110079237 CN102226051B (en) | 2011-03-30 | 2011-03-30 | Glaze coloring agent for waterborne woodenware coating and preparation method thereof |
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| CN 201110079237 CN102226051B (en) | 2011-03-30 | 2011-03-30 | Glaze coloring agent for waterborne woodenware coating and preparation method thereof |
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| CN102500538A (en) * | 2011-11-21 | 2012-06-20 | 南京林业大学 | Process method for fabricating open paint of solid wood composite door |
| CN102827547A (en) * | 2012-09-07 | 2012-12-19 | 鹤山市奎地涂料有限公司 | Aqueous antique paint |
| CN104140718A (en) * | 2014-07-17 | 2014-11-12 | 嘉丰木业（苏州）有限公司 | Preparation method of mixed color toner for archaized floor |
| CN104910747A (en) * | 2015-05-27 | 2015-09-16 | 天津市美冠科技有限公司 | Water-based glaze and preparation method thereof |
| CN105153856A (en) * | 2015-09-25 | 2015-12-16 | 中华制漆(新丰）有限公司 | Water-based color removing agent and preparation and use method and application thereof |
| CN106378292A (en) * | 2016-08-30 | 2017-02-08 | 章太平 | American antique waterborne coating process |
| CN107474706B (en) * | 2017-08-03 | 2019-11-22 | 广州立邦涂料有限公司 | A kind of house ornamentation aqueous wooden ware wiping color base material and preparation method thereof |
| CN108727982A (en) * | 2018-04-18 | 2018-11-02 | 佛山市高明富力特化工有限公司 | A kind of imitative wood grain effect paint and preparation method thereof and application method |
| CN109760160A (en) * | 2019-01-22 | 2019-05-17 | 常州双元职业技能培训中心 | A kind of high steady timber wiping stain |
| CN113956727B (en) * | 2021-10-29 | 2023-02-17 | 广东华润涂料有限公司 | Colorant composition and coated article |
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